Process of treating leather with alkoxylated mannich compositions,and optionally tanning agents,and products thereof

ABSTRACT

LEATHER TREATING AGENTS WHICH ARE (A) REACTION PRODUCTS OF HYDROXYL CONTAINING NITROGEN COMPOUNDS AND ISOCYANATE TERMINATED URETHANE PREPOLYMERS OR (B) REACTION PRODUCTS OF HYDROXYL CONTAINING NITROGEN COMPOUNDS AND ISOCYANATE TERMINATED URETHANE PREPOLYMERS FURTHER REACTED WITH ACIDS OR QUATERNIZING REAGENTS TO PRODUCE AN ACID ADDITION SALT OR A QUATERNARY AMMONIUM SALT.

United States Patent U.S. Cl. 8-94.21 6 Claims ABSTRACT OF THEDISCLOSURE Leather treating agents which are (a) reaction products ofhydroxyl containing nitrogen compounds and isocyanate terminatedurethane prepolymers or (b) reaction products of hydroxyl containingnitrogen compounds and isocyanate terminated urethane prepolymersfurther reacted with acids or quaternizing reagents to produce an acidaddition salt or a quaternary ammonium salt.

This application is a divisional application of Ser. No. 573,789,Sellet, filed Aug. 22, 1966, now abandoned.

The present invention relates to novel treating agents, which are (a)hydroxyl containing nitrogen compounds, (b) reaction products ofhydroxyl containing nitrogen compounds with acids or quaternarizingagents, (c) reaction products of hydroxyl containing nitrogen compoundsand isocyanate terminated urethane prepolymers or (d) reaction productsof hydroxyl containing nitrogen compounds, isocyanate terminatedurethane prepolymers with acids or quaternizing agents and theirutilization in the treatment of fibrous, porous and nonporoussubstrates.

It is an object of the present invention to provide for novel treatingagents, especially for fibrous, porous and nonporous substrates. Suchnovel treating agents include hydroxyl containing nitrogen compounds aswell as their reaction products with isocyanate terminated urethaneprepolymers obtained by reaction of polyethers such as polyoxyalkylenepolyols, polyols such as alkylene polyols and polyesters having at leasttwo terminal hydroxyl groups with polyisocyanates. A further object isto pro vide for novel treating agents which are acid addition orquaternary ammonium salts of the hydroxyl containing nitrogen compoundsor their reaction products with isocyanate terminated urethaneprepolymers. Still another object is to provide for novel treatingagents which when utilized in connection with fibrous, porous ornonporous substrates bring about enhanced properties of such substrates.Another object is to provide procedures for preparing these noveltreating agents. A still further object is to provide for improvedleather treating agents which impart improved properties when applied tosaid substrates in such diverse operations as tanning, retanning,dyestutf and pigment :binding, dyeing, dispersing, coating andfinishing, as well as in applications where treating agent propertiessuch as dispersibility, dyeability, elongation, flexibility, adhesion,antistatic, abrasion resistance, bonding and the like are desired. Otherobjects will become apparent from the detailed description givenhereinafter. It is intended, however, that the detailed description andspecific examples do not limit the invention but merely indicatepreferred embodiments thereof since changes and modifications within thescope of this invention will become apparent to those skilled in theart.

The above as well as other objects have been unexpectedly andsuccessfully achieved in the following man- 3,674,415 Patented July 4,1972 ner. I have prepared and utilized in the treatment of variousfibrous, porous and nonporous substrates such as films, sheets, solids,fibers, and like materials, treating agents which can be broadlydescribed as hydroxyl containing nitrogen compounds which are thealkoxylation products of polyhydroxy compounds containing methylenicalkanolamine radical substituents such as those obtained when carryingout the Mannich reaction using aryl hydroxy compounds, aldehyde oraldehyde liberating compositions and alkanolamines. Likewise I have alsoprepared treating agents, which are the reaction products of theabove-described hydroxyl containing nitrogen compounds and isocyanateterminated urethane prepolymers. Also I have prepared and used astreating agents, addition salts and quaternary ammonium salts of both(a) the hydroxyl containing nitrogen compounds and (b) their reactionproducts with isocyanate terminated urethane prepolymers, By the termisocyanate terminated urethane prepolymer is meant those productsobtained by reaction of polyethers such as polyoxyalkylene polyols,polyols such as alkylene polyols and polyesters having at least twoterminal hydroxyl groups with organic polyisocyanates. Such isocyanateprepolymers are isocyanate terminated urethane prepolymers, i.e., thesole reactive groups in the prepolymer are isocyanate groups. By theterm polyether is meant polyoxyalkylene polyols containing at least twoterminal hydroxyl groups. By the term polyols is meant alkylene polyolscontaining at least two terminal hydroxyl groups. By the term polyesteris meant the reaction products of polycarboxylic acids or theiranhydrides with polyoxyalkylene polyols or alkylene polyols wherein thereaction products contain at least two terminal hydroxyl groups.

The treating agents of the present invention include hydroxyl containingnitrogen compounds which are alkoxylated derivatives of Mannich Basecompounds. Such Mannich Base compounds are the reaction products of (1)a phenol having at least one reactive hydrogen atom present in thephenol nucleus, (2) at least one aldehyde or aldehyde liberatingcomposition and (3) at least one alkanolamine such as a monoalkanolamineor dialkanolamine wherein the alkylene group contains at least twocarbon atoms. The (2) aldehyde or aldehyde liberating composition and(3) alkanolamine are present in approximately equimolar amounts withrespect to each other. Further, there is present one mole of the (2)aldehyde or aldehyde composition and one mole of (3) alkanolamine foreach reacting reactive hydrogen atom present in the phenol nucleus. Byreacting reactive hydrogen atoms present in the phenol nucleus is meantthe number of reactive hydrogen atoms in the phenol nucleus which arechosen for reaction with aldehyde and alkanolamine in the Mannichreaction. For example, phenol has three reactive hydrogen atoms. One maychoose to react one, two

or three of these reactive hydrogen atoms by the Mannich reaction. Thephenol nucleus in a 2,4- or 2,6-disubstituted phenol has only onereactive hydrogen atom so one can only choose to react the only reactivehydrogen. The phenol nucleus in a complex phenol such as a Novolak maycontain n reactive hydrogen atoms so one can choose to react from one ton reactive hydrogen atoms in the phenol nucleus. The manner in which areactive hydrogen atom in the phenol can be reacted can be varied. Forexample, a reactive hydrogen atom in the alkanolamine can be reactedwith the aldehyde and the resulting reaction product then can be reactedwith the reactive hydrogen atom in the phenol nucleus. The reactivehydrogen atom in the phenol nucleus can be reacted with the aldehyde oraldehyde composition to obtain an alkylolated phenol which can then bereacted with a reactive hydrogen atom in the alkanolamine. The phenol,alkanolamine and aldehyde or aldehyde composition can be combined andreacted in one step. The order in which the phenol, alkanolamine andaldehyde or aldehyde composition are reacted in the Mannich reaction isdetermined by factors such as convenience, properties of the reactants,properties desired in the Mannich Base compound or the like.

The hydroxyl containing nitrogen compounds described above can be usedas a treating agent itself or can be modified to produce other types oftreating agents. For example, hydroxyl containing nitrogen compounds canbe reacted with isocyanate terminated urethane prepolymers to producetreating agents which contain urethane linkages. Preparation of suchtreating agents involves reaction of reactive isocyanate groups withhydroxyl groups present in the hydroxyl containing nitrogen compounds.Furthermore such treating agents, e.g., the hydroxyl containing nitrogencompounds as well as their reaction products with isocyanate terminatedurethane prepolymers, can be reacted with acids or quaternizing reagentsto produce treating agents. Reaction of the acid or quaternarizingreagent is with the nitrogen atoms present in the treating agent. Theacid or quaternizing reagent is employed in an amount suflicient toreact with at least one of the nitrogen atoms present in the treatingagent. When desired, all of the nitrogen atoms in the treating agent canbe converted to acid addition salts or quaternary nitrogen atoms byemploying sufiicient acid or quaternizing reagent. The foregoingtreating agents as well as processes for their manufacture and theiruses are described in greater detail below.

These novel treating agents have outstanding properties which are inpart attributed to the hydroxyl containing nization of the reactionproducts of these hydroxyl compounds can be obtained by alkoxylation ofthe Mannich reaction products of aryl hydroxyl compounds such as phenolswith aldehydes and alkanolamines so as to provide for at least onealkoxylated substituent for each phenolic hydroxyl group present inMannich Base compound, i.e., there may optionally be additionalalkoxylated substituents on such hydroxyl group and also one or more oneach alkanol group present in the alkanolamine radical substituentsattached to the alkoxylated phenolic nucleus. These hydroxyl containingnitrogen compounds are described below in the section entitled HydroxylContaining Nitrogen Compounds. Hydroxyl containing nitrogen compoundsuseful in the present invention include alkoxylated phenols having atleast one methylenic dialkanolamine radical substituent, methylenicoxyalkylated dialkanolamine radical substituent, methylenicmonoalkanolarnine radical substituent or methylenic oxyalkylatedmonoalkanola-mine radical substituent attached to the alkoxylatedphenolic nucleus. Useful alkoxylated phenols include alkoxylatedalkylphenols, alkoxylated polynuclear phenols, alkoxylated phenylphenols, alkoxylated phenols linked by alkylene bridges, alkoxylatedfused phenols and the like having at least one alkoxylated phenolichydroxyl group and at least one methylenic alkanolamine substituent orat least-one oxyalkylated methylenic alkanolamine radical substituent.It is to be understood that mixtures of the abovementioned hydroxylcontaining nitrogen compounds can be used in the preparation of thetreating agents disclosed in this invention. Treating agents can also beprepared by reaction of isocyanate terminated urethane propoly mers withthese hydroxyl containing nitrogen compounds and by quaternization ofthe reaction products of these hydroxyl containing nitrogen compoundsand isocyanate terminated urethane prepolymers or by addition of acidsto these reaction products to form salts. Further, treating agents canbe prepared by quaternization of the hydroxyl containing nitrogencompounds themselves or by addition of acids to form salts.

These treating agents are unique in that they are not sensitive to waterand can be applied from aqueous solutions or disperisons. A furtheradvantage of these treating agents is that they can be prepared in theform of quaternary ammonium salts or acid addition salts and applied tosubstrates in the form of solutions or dispersions. The treating agentsmay be used directly or in the form of their salts or quaternaries. Theymay be formulated with acids, surfactants, solvents and the like toobtain formulations for applications where specific requirements such aswater-solubility, solvent solubility, dispersibility or the like arerequired.

Since the treating agents enhance properties such as film forming,coating, dyeability, dispersibility, adhesion, abrasion resistance,washfastness, antistatic, light stability and other properties as wellas acting as carriers and/ or binders for pigments and dyestuffs, it isa definite advantage to be able to vary the nature and the properties ofthe hydroxyl containing nitrogen compounds employed as treating agentsand in the preparation of the treating agents disclosed in thisinvention as described hereinafter.

HYDROXY L CONTAINING NITROGEN COMPOUNDS The hydroxyl containing nitrogencompounds useful in the present invention are prepared by reacting (a)at least one mole of an alkylene oxide or mixtures thereof wherein eachalkylene group in the oxide contains from 2 to 57 carbon atoms with (b)at least each phenolic hydroxyl group present in an aromatic MannichBase compound having at least one phenolic hydroxyl group and at leastone methylenic alkanolamine radical substituent attached to an aromaticring present in the Mannich Base compound. Reaction of alkylene oxidewith the phenolic hydroxyl groups in the Mannich Base compounds convertsthese groups to hydroxyalkyl phenoxy groups. When more than one mole ofalkylene oxide per each phenolic hydroxyl group present in the aromaticMannich Base compound is employed, the additional alkylene oxide reactswith the hydroxyalkyl phenoxy groups as well as the alkanol groups ofthe methylenic alkanolamine radical substituents present in the MannichBase compound. Thus, the hydroxyl groups present in the hydroxycontaining nitrogen compound can contain alkylene oxide orpolyoxyalkylene chains.

Aromatic Mannich Base compounds useful in preparing the abovementionedhydroxyl containing nitrogen compounds can be obtained by the Mannichreaction. The Mannich reaction has ben described generally above and isdescribed in greater detail below. Preparation of Mannich Base compoundscan be achieved by the methods described below as well as the methodsgiven in US. Pat. No. 2,033,092, Bruson, Mar. 3, 1936; US. Pat. No.2,114,122, Bruson, Apr. 12, 1938 and US. Pat. No. 2,220,834, Bruson et211., Nov. 5, 1940. Formulas I to V inclusive illustrate the types ofMannich Base compounds obtained when from one to three moles offormaldehyde and from one to three moles of diethanolamine, present inapproximately equimolar amounts with respect to each other, arecondensed with one mole of phenol. For example, condensation of one moleof formaldehyde and one mole of diethanolamine with one mole of phenolyields nitrogen compounds of the type shown in Formulas I and II.

I) OH I CHzC HzOH CHzN CH GH OH and (1)11 i CH2CH2OH GH -N CHzCHzOHLikewise, when two moles of formaldehyde and two moles of diethanolamineare condensed with one mole of phenol, Mannich Base compounds of thetypes shown in Formulas III and IV are obtained.

(III) OH i CHzCHzOH CH2N CHzCHzOH H2CH2OH CHz-N CHzCHzOH and HOCHZCHICHzCHzOH N-CH CHz-N HOCHgCfi: CHzCHzOH When three moles of formaldehydeand three moles of diethanolamine present in equimolar amounts arecondensed with one mole of phenol, the Mannich Base compound shown inFormula V is obtained.

HOCHzCl-Iz I CHzCHzOH NCH CH2N HOCHzC: CHZCHQOH CHzCHzOH C Hz-N CHzCHzOHFormulas I to V inclusive illustrate various types of Mannich Basecompounds obtained in the Mannich reaction of formaldehyde anddiethanolamine with phenol. It is of course understood that, inpractice, the Mannich Base compounds are not necessarily obtained inpure form, but quite often are obtained as mixtures of compounds withone particular type predominating. Further, it is to be understood thatthe above and subsequent structural formulas are set forth herein tofacilitate an understanding of the present invention. They are not,however, to be construed as limiting the present invention to theirprecise structures.

Similar Mannich Base compounds are obtained when monoethanolamine,N-methyl monoethanolamine or N- ethyl monoethanolamine is substitutedfor diethanolamine in the Mannich reaction. Likewise alkanolamines suchas dipropanolamines, monopropanolamines, N-alkyl monopropanolamines,dibutanolamines, monobutanolamines, N-alkyl monobutanolamines,monohexanolamine, monododecanolamine, their isomers and higherhomologues or the like can be substituted for diethanolamine, e.g.,diisopropanolamine.

Aldehydes or aldehyde compositions which provide aldehydes containingfrom one to seven carbon atoms can be used in the Mannich reaction. Forexample, formaldehyde can be used in the form of 30 to 40% aqueoussolutions, 30 to 55% alcohol solutions with alcohols such as methanol,n-butanol, i-butanol or the like. Formaldehyde can also be used in anyof its polymeric forms such as paraformaldehyde, trioxane, hexamethylenetetramine or the like. Other aldehydes such as acetaldehyde,butyraldehyde, heptaldehyde, furfuraldehyde, chloral, alpha-ethylbeta-propylacrolein, benzaldehyde or the like can be substituted forformaldehyde in the Mannich reaction. Aldehyde compositions such asacetals which liberate such aldehydes can also be employed. Suchaldehyde compositions may also include aldehyde and hydrogen chloridemixtures wherein the phenol is chloromethylated and then reacted withalkanolamine to obtain Mannich Base compounds.

Phenols such as alkylphenols, polynuclear phenols, polyphenyl phenols,phenols linked by alkylene bridges (novolaks), fused phenols and thelike having at least one free phenolic hydroxyl group and at least onereactive hydrogen in the phenolic nucleus can be substituted for phenolin the Mannich reaction.

Mannich Base compounds similar to those shown in Formulas I to Vinclusive can be prepared from 3-alkylphenols such as 3-methylphenyl(m-cresol), 3-n-pentadecyl phenol, their isomers, homologues, mixtures,and the like by condensing one mole of 3-alkylphenol with from one tothree moles of an aldehyde and from one to three moles of alkanolamine,the aldehyde and alkanolamine being present in approximately equimolaramounts with respect to each other.

Other useful Mannich Base compounds can be prepared from 2-alkylphenols,4-alkylphenols, 2,4-dialkylphenols and 2,6-dialkylphenols by use of theMannich reaction. For example, 2-alkylphenols and 4-alkylphenols can bereacted with from one to two moles of an aldehyde and from one to twomoles of diethanolamine, the aldehyde and alkanolamine being present inapproximately equimolar amounts with respect to each other, to obtainMannich Base compounds having from one to two methylenic diethanolamineradicals. 2-alkylphenols which can be used in the preparation of MannichBase compounds include 2- methylphenol, Z-ethylphenol, 2-n-propylphenol,2-i-propylphenol, 2-n-butylphenol, 2-t-butylphenol, 2-n-pentylphenol,Z-n-hexylphenol, Z-n-heptylphenol, 2-n-octylphenol, 2-t-octylphenol,Z-n-nonylphenol, Z-i-nonylphenol, Z-n-decylphenol, 2-n-dodecylphenol,Z-n-tridecylphcnol, 2- n-tetradecylphenol, Z-n-pentadecylphenol,2-n-hexadecylphenol, 2-n-octadecylphenol, 2-n-nonadecylphenol,2-neicosylphenol, 2-n-docosylphenol, Z-n-triacontylphenol, theirisomers, their mixtures and the like. The corresponding4-n-alkylphenols, their isomers, their mixtures and the like can also beemployed. Such monoalkylphenols are well known in the art, particularly,those containing branched substituents and are used extensively in themanufacture of surfactants, antioxidants and the like. Many of thesealkylphenols can be prepared by alkylation of phenol with olefinscontaining from three to thirty carbon atoms. Usually alkylationprocedures produce mixtures of 2- and 4-alkylphenols. Alkylphenols canbe used in the form of these mixtures or the Z-al-kylphenols can beseparated from the 4-alkylphenols by distillation or other methods andused individually.

The corresponding 2,4-dialkylphenols and 2,6-dialkylphenols can beproduced by alkylation methods similar to those described above, thatis, by reaction of one mole of phenol with two moles of olefincontaining from three to thirty carbon atoms and employed in the Mannichreaction. It is to be understood that dialkylphenols having dissimilaralkyl groups can be employed. For example, dialkylphenols such as2-methyl-4-nonylphenol and 2-octy1- 4-methylphenol can be used. Suchphenols can be obtained by alkylation of the correspondingmethylphenols. Dialkylphenols obtained by these alkylation methods canalso be used as mixtures or the desired 2,4-alkylphenols may beseparated from the 2,6-dialkylphenols and used individually. Suchdialkylphenols contain only one reactive hydrogen atom and can reactwith only one mole of alkanolamine and one mole of aldehyde or aldehydecomposition in the Mannich reaction.

It is to be understood that olefins employed in the preparation of theabove alkylphenols can be either linear or branched chain olefins andthat mixtures of such olefins can be used. Generally, a-olefins arepreferred because of their high reactivity. Linear olefins obtained bythe reaction of ethylene with metal alkyls such as the Ziegler typecompounds or those obtained in the wax cracking of fats are particularlyuseful in the preparation of alkylphenols.

Other phenols useful in the Mannich reaction include ophenylphenol andp-phenylphenol as well as phenols linked to aromatic groups by alkylenebridges such as those in a-methylbenzyl-ophenol anda-dimethylbenzyl-o-phenol.

These phenols can be alkylated to produce other types of phenols whichare useful in the Mannich reaction. Formula VI illustrates a MannichBase compound obtained by the reaction of one mole oftx-methylbenzyl-o-phenol, one mole of formaldehyde and one mole ofdiethanolamine which is useful as a hydroxyl containing nitrogencompound in the present invention.

(VI) omomon Additional examples of useful phenols are polynuclearphenols, polyphenyl phenols, phenols linked by alkylene bridges(novolaks), fused phenols and the like such as diphenol,4,4'-dihydroxy-diphenyl-dimethylmethane 4,4'-dihydroxy-diphenyl-methylmethane, 4,4 dihydroxy-diphenylmethane, l-naphthol, Z-naphthol, and thelike having at least one reactive hydrogen therein.

Formula VII illustrates a Mannich Base compound obtained by bridging twophenols containing methylenic diethanolamine radicals by reaction withformaldehyde. This Mannich Base compound in which two phenolic nuclei ortwo phenolic moieties are linked by an alkylene bridge is particularlyuseful in the present invention. The Mannich Base compound shown inFormula VII contains two reactive hydrogen atoms which can be furthersubstituted by the Mannich reaction if desired.

OH HO CH2C H2 I C H2O HzOH Phenols having two free phenolic hydroxylgroups and having at least one reactive hydrogen in the phenolic nucleussuch as catechol, resorcinol, hydroquinone and the like can also beemployed in the Mannich reaction to produce Mannich Base compoundsuseful in the present invention.

Thus, as shown by the aforedescribed examples of phenols which areuseful herein, it is clear that wherever the term phenols is used, it isintended to encompass the phenols of the kind described above inaddition to phenol itself and including phenols having one, two or morephenolic nuclei or moieties.

The above Mannich Base compounds can be prepared in the following mannerby reaction of alkanolamine, aldehyde and phenol at about 5 C. to about110 C. Usually from one to three moles of the desired alkanolamine and asolvent such as water or a monohydric alcohol are charged to a reactorequipped with agitator, reflux condenser and provision for externalheating and cooling. The amine solution is cooled to about 5 C. to about15 C. and a solution of from one to three moles of an aldehyde, saidaldehyde being present in approximately equimolar amount with respect tothe alkanolamine, in a solvent such as water or a monohydric alcoholperiod of from one-half to two hours. The temperature is maintainedbelow about 15 C. during this addition. A solution containing one moleof the desired phenol in solvent such as water or a monhydric alcohol isthen added to the reaction mixture over a period of from onehalf to twohours while the temperature is maintained in the range of from about 15C. to about 40 C. The resulting reaction mixture is then stirred for anadditional fifteen minutes to two hours at a temperature of from about15 C. to about 40 C., then heated to from about 60 C. to about C. andheld at this temperature for from one to four hours to completereaction. The resulting product which is the Mannich Base compound isthen heated under vacuum to remove Water, monohydric alcohols and othervolatile materials by distillation. Vacuum distillation is continued atabout 90 C. to about C. until the water content of the resulting MannichBase compound is about 0.5% or less by weight.

Mannich Base compounds prepared by the foregoing procedure may containavailable reactive hydrogen atoms in the phenolic moiety or phenolicmoieties present in the Mannich Base compound. Such reactive hydrogenatoms will be in unsubstituted ortho and para positions in the phenolicmoieties. It is to be understood that when said phenol in the MannichBase compound contains a plurality of phenolic moieties, there will be amaximum of two available reactive hydrogens in the first phenolic moietyand only one in each of the remaining phenolic moieties. Formula VIIIillustrates a Mannich Base compound in which the phenol has threephenolic moieties and four available hydrogens in the ortho and parapositions.

vnr on OH l CHQCHQOH Likewise, Formula IX illustrates a Mannich Basecompound in which the phenol has four phenolic moieties and fiveavailable reactive hydrogens in the ortho and para positions.

CHzCHsOH It is of course understood that replacement of availablehydrogens with methylenic alkanolamine radicals in the phenolic moietywill reduce available unreacted hydro gen atoms for subsequent reaction.When desired, the above Mannich Base compound procedure may be employedto replace any available reactive hydrogen atoms in the Mannich Basecompound with methylenic alkanolamine radicals. Likewise, such reactivehydrogen atoms can be reacted with bridging agents such as aldehydes,aldehyde compositions which liberate aldehydes and the like to producedimers, trimers and higher polymers of the Mannich Base compounds.

The above described Mannich Base compounds can be prepared by proceduresother than the Mannich reaction, e.g., chloromethylation and conversionof the resulting chloro derivatives to alkanolamines. Such proceduresare equally useful in preparing Mannich Base compounds and can beemployed to prepare isomers and homologues not readily obtainable by theMannich reaction. For this reason, the present invention is not to beconstrued as limiting useful Mannich Base compounds to only thosecompounds obtained by the Mannich reaction. The term Mannich Basecompound as used herein encompasses those compounds containing at leastone phenolic byis added to the cooled alkanolamine solution over a 75droxyl group and at least one methylenic alkanolamine group attached toan aromatic nucleus present in the compound regardless of theirpreparation.

Hydroxyl containing nitrogen compounds useful in the present inventionare prepared by condensing at least one mole of an alkylene oxidecontaining from two to 57 carbon atoms with each phenolic hydroxyl grouppresent in the Mannich Base compound. Formula X illustrates an alkyleneoxide adduct obtained when one mole of an alkylene oxide, R containingfrom two to 57 carbon atoms is condensed with a Mannich Base compoundwherein R and R are alkylene groups containing from two to twelve carbonatoms and R and R can be alike or difierent.

when the alkylene oxide adduct shown in Formula X is further condensedwith an alkylene oxide, R 0 containing from two to 57 carbon atoms, anadduct of the type shown in Formula X1 is obtained:

wherein R and R are alkylene groups containing from two to twelve carbonatoms and R and R can be alike or different; and the value of n may varyfrom 0 to about 150 depending on the number of moles and the type of thealkylene oxide employed and may be a fractional quantity. For example,for n to be greater than 1, R 0 must be derived from ethylene oxide,propylene oxide, butylene oxide or styrene oxide. It is to be understoodthat Formulas X and XI are presented merely to illustrate two of thetypes of hydroxyl containing nitrogen compounds obtained by condensingone or more alkylene oxides with a Mannich Base compound of the typeshown in Formula H above and are not to be construed as limiting thisinvention. Similar compounds can be prepared by alkoxylation of theother Mannich Base compounds shown in the formulas above, that is,Formulas I and III-1X (inclusive) as well as mixtures of such compounds.It should be understood that when additional alkylene oxide, i.e., inexcess of one mole per phenolic hydroxyl present in the phenolicnucleus, is introduced onto the Mannich Base compound, such alkyleneoxide may distribute itself upon the Mannich Base compound in variousways. For example, instead of the alkylene oxide, R 0 adding on thealkylene oxide, R 0 and on to the hydroxyl groups of both of the alkanolgroups of Formula XI, it can add on in other ways. For example, thealkylene oxide R 0 can add entirely on to the alkylene oxide R 0 orentirely upon one or both of the hydroxy groups of the alkanolamines.However, it is most likely that the alkylene oxide R 0 adds uniformly onto all of the available hydroxyl groups, i.e., those from the prioralkylene oxide addition and from the alkanolamines. It is well knownthat the alkylene oxides condense preferentially with the phenolicgroups, then with the primary alkanol groups and then with any secondaryalkanol groups present. Hence, in preparing the hydroxyl containingcompounds, the phenolic hydroxyl will react with the alkylene oxides inall cases. The large variety of types of alkoxylated Mannich Basecompounds which can be employed precludes presentation of a generalformula to cover all various types of useful hydroxy containing nitrogencompounds. The condensations between the alkylene oxides and MannichBase compounds are carried out at a temperature of from about 30 C. toabout 200 C. and the Mannich Base is dehydrated prior to condensation sothat it has a water content of less than 0.5% by weight. When desired,an alkoxylation catalyst such as an alkali metal hydroxide, a basiccatalyst or other suitable alkoxylation catalyst may be used. Typicalcatalysts include sodium hydroxide, sodium methylate, potassiumhydroxide, boron trifluoride etherate and the like. These catalysts areemployed in concentrations from about 0.01% by weight to about 1.0% byweight based on the weight of Mannich Base compound. Such alkoxylationcatalysts are well known in the art. Frequently, the amine groupspresent in the Mannich Base compound provide suflicient basicity topromote the condensation of the phenolic hydroxyl groups with thealkylene oxide and catalyst addition will not be necessary during theinitial phase of the condensation. However, if the reaction is sluggishat any point during the condensation, the reaction rate can be promotedby the addition of from about 0.01% by weight to about 1.0% by weight ofone of the above-mentioned catalysts. Since the phenolic hydroxyl groupsare more reactive than the hydroxyl groups present in the alkanolgroups, the phenolic hydroxyl groups condense with alkylene oxide firstto form hydroxyalkyl phenoxy groups. The alkylene oxide then condenseswith free hydroxyls in the hydroxy alkyl groups and the free hydroxylspresent in the alkanol groups to form an alkylene oxide orpolyoxyalkylene chain so that each chain is terminated at one end by afree hydroxyl group. The resulting hydroxyl containing nitrogencompounds contain at least two free and reactive terminal hydroxylgroups. Such hydroxyl containing nitrogen compounds are, in eifect,aromatic polyols having diol, triol, tetrol, pentol or higher hydroxylfunctionalities.

The alkoxylation procedures employed in preparing these hydroxylcontaining compounds are well known. Such procedures have been usedextensively commercially in the preparation of nonionic surfactants,polyethers for polyurethane resins and other alkylene oxide derivatives.Typical alkoxylation procedures are described in U.S. Patent No.2,213,477, Steindorfi et a1. (Sept. 3, 1940).

a As examples of alkylene oxides which may be employed in alkoxylationof Mannich Base compounds, any alkylene oxide containing from two to 57carbon atoms may be used. Such alkylene oxides include ethylene oxide,propylene oxide, butylene oxide, hexylene oxide, octylene oxide,decylene oxide, dodecylene oxide, styrene oxide, glycidol, theirisomers, their mixtures and the like. Other alkylene oxides includedicyclopentadiene dioxide, limonene dioxide, 3,4-epoxy 6methylcyclohexylmethyl-3,4- epoxy-6-methylcyclohexane-carboxylate, thediepoxide of the diglycidyl derivative of4,4'dihydroxy-diphenyl-dimethyl methane, epoxidized soya bean oil, e.g.,containing 7% by weight of oxide, monoglycidyl ethers of alcohols suchas Epoxide 7, 8, 44 and 45 produced by Procter & Gamble Co., Cincinnati,Ohio, and the like. Epoxide 7 is a monoglycidyl ether of a mixture of Cto C alcohols containing a total of from about 11 to 13 carbon atoms andhaving an oxide content of about 7% by weight. Epoxide 8 is amonoglycidyl ether of a mixture of C to C alcohols, containing a totalof from about 15 to 17 carbon atoms and having an oxide content of about5.6. Epoxide 44 is a monoglycidyl ether of a mixture of C alcohols,containing an average of 17 carbon atoms and having an oxide content ofabout 5.2% by weight. Epoxide 45 is a monoglycidyl ether of a mixture ofC to C alcohols containing a total of from about 19 to 21 carbon atomsand having an oxide content of about 4.3% by weight. If desired,alkylene oxides such as ethylene oxide, propylene oxide, butylene oxideand styrene oxide may be condensed sequentially. That is, the hydroxylgroups are reacted with one alkylene oxide and the resulting condensatesreacted or capped with a dissimilar alkylene oxide. Likewise, thehydroxyl groups can be reacted with a plurality of moles of onealkylene. oxide such as ethylene oxide, propylene Oxide, butylene oxideand styrene oxide to form a polyoxyalkylene block and then with aplurality of moles of a second alkylene oxide such as ethylene oxide,propylene oxide, butylene oxide and styrene oxide to form a secondpolyoxyalkylene block so that each hydroxyl group is a chain whichcontains at least two dissimilar polyoxyalkylene blocks.

It is of course understood that the addition of alkylene oxides to theMannich Base compound can be carried out either before or after theMannich Base compound is reacted with the prepolymer. When carried outafter reaction with the prepolymer, it is clear that there are fewerhydroxyl groups available for reaction.

PREPARATION OF PREPOLYMERS Polyisocyanates are used in the form ofisocyanate terminated urethane prepolymers which are prepared byreacting one or more polyisocyanates with a hydroxyl terminated compoundhaving at least two terminal bydroxyl groups such as a polyol which isan alkylene polyol, a polyether which is a polyoxyalkylene polyol or apolyester. Such prepolymers are isocyanate terminated adducts ofpolyisocyanates and a hydroxyl terminated compound having at least twoterminal hydroxyl groups such as a polyol, polyether or a polyester. Thesole reactive groups in these isocyanate terminated prepolymers arereactive isocyanate groups. Such isocyanate terminated urethaneprepolymers are well known in the art and are frequently used instead ofpolyisocyanates because the prepolymers are less toxic and have lowervolatilitics than polyisocyanates per se.

Isocyanate terminated urethane prepolymers are prepared under anhydrousconditions by mixing one or more of the hydroxy terminated compoundswith an excess of an organic polyisocyanate and heating the resultingmixture to a temperature of from about 50 to about 100 C. to form aprepolymer whose sole reactive groups are reactive isocyanate groups. Analternate procedure is to react a polyisocyanate with a molar excess ofa polyol, a polyether or a polyester having at least two terminalhydroxyl groups, then cap the resulting reaction product, that is, reactit with additional organic polyisocyanate so that the sole reactivegroups in the prepolymer are reactive isocyanate groups. By the termpolyol or alkylene polyol is meant any hydroxyl containing alkylenecompound which has diol, triol or higher hydroxyl functionality and hasat least two terminal hydroxyl groups. By the term polyether oroxyalkylene polyol is meant any hydroxyl containing polyether compoundhaving diol, triol or higher hydroxyl functionality and having at leasttwo terminal hydroxyl groups. The polyesters, likewise, should have atleast two terminal hydroxyl groups. By an excess polyisocyanate is meantat least 1.1 isocyanate groups for each terminal hydroxyl .group. Thepreferred ratio of equivalents of isocyanate groups to hydroxyl groupsin the prepolymer should be about 2:1. The quantity of reactiveisocyanate in the prepolymer can also be expressed on a weight basis.Thus, for example, a prepolymer prepared from tolylene diisocyanate anda polyoxyethylene glycol having an average molecular weight of 300 hasan isocyanate content of 14.3% by weight. It is clear that as the weightof the polyoxyethylene glycolincreases, the weight percent of isocyanatein the prepolymer will decrease. Thus, a prepolymer from tolylenediisocyanate and a polyoxyethylene glycol having an average molecularweight of 3350 will have an isocyanate content of,2. 3% by weight. Whenthe prepolymer is the reaction product of a polyol, that is, an alkylenepolyol such as trimethylol propane and a polyisocyanate such astolylene. diisocyanate, the prepolymer is customarily described as thereaction product of about one mole of trimethylol propane and aboutthree moles of tolylene diisocyanate and the isocyanate content is notgiven. Examples of polyol prepolymers include the reaction product oftolylene diisocyanate with trimethylol propane at an NCO/OH ratio of 2:1(Mondur CB) and the reaction product of tolylene diisocyanate with1,2,6-hexanetriol at an NCO/ OH ratio of 2:1. Such prepolymers are wellknown and have been used extensively. Likewise, when the prepolymer isthe reaction product of a polyester and-"a polyisocyanate, it isdescribed in terms of the polyester and polyisocyanate and theisocyanate content, is not given. Such prepolymers are classified aspolyether prepolymers, polyol prepolymers and polyester prepolymers andgenerally as isocyanate terminated urethane prepolymers or prepolymersbecause of their extensive use in the art.

Representative polyisocyanates, which can be employed in the productionof prepolymers, include tolylene-2,4-diisocyanate,tolylene-2,6-diisocyanate,

tolylene diisocyanate (65% 2,4; 35% 2,6), tolylene diisocyanate (65%2,4; 35% 2,6), 1,6-hexamethylenediisocyanate (HDI),1,4-tetramethylenediisocyanate, hexamethylene diisocyanate,

1 10-decamethylenediisocyanate, 1,5-naphthalenediisocyanate (NDI),cumene-2,4diisocyanate, 4-methoxy-1,3-phenylenediisocyanate,4-chloro-l,3-phenylenediisocyanate, 4-bromo-1,3-phenylenediisocyanate,4-ethoxy-1,3-phenylenediisocyanate, 2,4'-diisocyanatodiphenylether,

diphenyl methane-4,4'-diisocyanate (MDI), 5,6-dimethyl1,3-phenylenediisocyanate, 2,4-dimethyl-1,3-phenylenediisocyanate, 4-isopropyl-1,3-phenylene diisocyanate,4,4'-diisocyanatodiphenylether, benzidinediisocyanate,

o-nitrobenzidene diisocyanate, 4,6-dimethyl-l,3-phenylenediisocyanate,9,l0anthracenediisocyanate, 4,4-diisocyanatodibenzyl,3,3'-dimethyl-4,4-diisocyanatodiphenylmethane, I2,6-dimethyl-4,4'-diisocyanatodiphenyl,' 2,4-diisocyanatostiblene,4,4'-dipl1enyl diisocyanate (XDI) 3,3'-dimethyl-4,4-diphenyldiisocyanate (TODI), 3,3-dimethoxy-4,4-diphenyl diisocyanate (DA-DI), 1,4'anthracenediisocyanate, mesitylene diisocyanate,

durylene diisocyanate, 2,5-fluorenediisocyanate,1,8-naphthalenediisocyanate, 2,6-diisocyanatobenzofuran,2,4,6-tolenetriisocyanate,

tritolylmethane triisocyanate,

2,4,4-triisocyanatophenyl ether and the like. Another useful isocyanate(PAPI-l) has the general formula NCO 13 where n has an average value ofabout 1. Mixtures of polyisocyanates may also be used.

Typical examples of isocyanate terminated urethane prepolymers includethese formed by reaction of tolylene diisocyanates and polyethers(polyoxyalkylene polyols). Polyethers used in these prepolymers may haveaverage molecular weights of about 136 to 5000 and preferably 600 to4000 and include, for example, polyoxyethylene glycol having a molecularWeight of 1540, polyoxypropylene glycol having a molecular weight of1025, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, polyoxynonamethylene glycol,polyoxydecamethylene glycol, polyoxydodecamethylene glycol and mixturesthereof. Polyoxyalkylene glycols containing several different radicalsin the molecular chain such as, for example, the compound wherein n isan integer greater than 4 can also be used. For example, polyacetalshaving hydroxyl groups and molecular weights of about 136 or more can beprepared when an aldehyde and an alcohol such as formaldehyde andethylene glycol are reacted.

Other polyoxyalkylene polyols, which can be employed in the preparationof the polyether prepolymers, include those prepared by reaction of1,2-alky1ene oxides such as ethylene oxide, propylene oxide, butyleneoxide, their mixtures and the like with polyhydroxy compounds such asglycerol, hydroxyl containing glycerides, trimethylolethane,trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitol, mannitol and the like,glucosides such as methyl, ethyl, propyl, butyl and 2-ethylhexylarabinsoide, xyloside, fructoside, glucoside, rhammoside and sucrose.For example, an ethylene oxide adduct of glycerol having an averagemolecular weight of 2000 can be used. A propylene oxide adduct oftrimethylolpropane terminated with ethylene oxide to obtain a productwith primary hydroxyl groups having an average molecular weight of 4500can also be employed. Likewise, an ethylene oxide adduct ofpentaerythritol having an average molecular weigth of 3000 can be used.A propylene oxide adduct of 1,2,6-hexanetriol having an averagemolecular weight of 1000 can be employed. Polyoxyalkylene polyolsobtained by reacting alkylene oxides with mononuclearpolyhydroxybenzenes such as resorcinol, pyrogallol, phloroglucinol,hydroquinone, 4,6-di-t-butylcatechol, catechol, orcinol, and otheralkylated polyhydroxy benzenes are also useful. Likewise polyoxyalkylenepolyols prepared by reacting alkylene oxides with fused ring systemssuch as 3-hydroxy- Z-naphthol, 6,7 dihydroxy 1 naphthol, 2,5 dihydroxylnaphthol, 9,10 dihydroxyanthracene, 2,3 dihydroxyphenanthrene and thelike can be used.

Other polyoxyalkylene polyols which can be employed include thoseobtained by reacting 1,2-alkylene oxides or mixtures thereof withpolynuclear phenols such as the various di-, triand tetraphenolcompounds in which phenols are attached by means of single bonds or byan aliphatic hydrocarbon radical.

Another particularly useful group of polyoxyalkylene polyols which canbe employed are the alkylene oxide adducts of the novolaks. Theseproducts are believed to be mixtures of polynuclear compounds of thediphenylmethane type of structure such as 4,4 dihydroxydiphenylmethaneand 2,4 dihydroxydiphenylmethane formed by the Baeyer reaction of phenoland formaldehyde. In a typical synthesis, novolaks are prepared bycondensing one mole of a phenol, such as phenol, cresol or otheralkylphenol with 0.8 mole of an aldehyde such as formaldehyde orfurfuraldehyde under acidic conditions at temperature of from 160 C. to170 C. These polynuclear phenols frequently contain 4 to 8 units and maycontain 12 or more units. They are non-curable thermoplastic resins.

Further included are the polyoxyalkylene polyols having nitrogen bridgesprepared by reacting one or more of the alkylene oxides described abovewith ammonia or acyclic polyamines such as ethylenediamine,propylenediamine, butylenediamine, pentylenediamine, hexylenediamine,octylenediamine, nonylenediamine, decylenediamine; polyalkylenepolyamines such as diethylenetriamine, triethylenetriamine,tetraethylene pentamine, and the like. A particularly suitablepolyoxyalkylene polyol is the propylene oxide addition product ofdiethylenetriamine represented by the formula:

wherein n represents an integer which provides an average molecularweight of 300 or more.

Other suitable polyoxyalkylene polyols include the 1,2- alkylene oxidederivatives of mononuclear primary amines such as 0-, m-, andp-phenylenediamine; 2,4- and 2,6-diaminotoluene; 2,6 diamine-p-xylene;4,6 diamino-m xylene; 2,4 diamino-m-xylene; 3,5 diamino-o-xylene;isohexyl-p-phenylenediamine; 3,5 diaminotoluene; and the like;polynuclear and fused aromatic polyamines such as 1,4naphthylenediamines; 1,5 naphthylenediamine; 1,8 naphthylenediamine;benzidine; toluidine; 4,4- methylenedianiline; 3,3 dimethoxy 4,4biphenyldiamine; 3,3 dichloro 4,4 biphenylidiamine; 3,3- dimethyl 4,4biphenyldiamine; 4,4 ethylenedianiline; 4,4 ethylidenedianiline; 1fiuorenamino; 2,5 fluorenediamine, 2,7 fiuorenediamine; 1,4anthradiamine; 3,3 biphenyldiamine; 3,4 biphenyldiamine; 9,10diaminophenanthrene; 4,4-diaminobenzene and the like.

Higher functional monoand polynuclear polyamines can also be reactedwith 1,2-alkylene oxides to provide useful polyoxyalkylene polyols.These amines include 2, 4,6 triaminotoluene, 2,3,5 triaminotoluene; 5,6diaminoacenaphthalene, 4,4',4 methylidynetrianiline, 3,5 diaminobenzoicacid, triaminodiphenyl ethers and sulfides such as 2,4,4triaminodiphenyl ether, 2,3',4- triamino 4' methoxydiphenyl ether, thecorresponding sulfides and the like; polyamines obtained by interactionof aromatic monoamines with formaldehyde or other aldehydes, forexample:

wherein R is hydrogen or an alkyl group.

Polyoxyalkylene polyols having sulfur bridges include the condensationproducts of thioglycol with itself or with other polyhydric alcoholssuch as ethylene glycol, diethylene glycol, trimethylolpropane and thelike. Such polyols can also be condensed with the abovementionedaromatic amines and phenols. Other suitable polycondensation productshaving sulfur and nitrogen bridges includes those obtained by reactionof thioglycol with aromatic amines such as xylidene, toluidines orreaction products of these aromatic amines with alkylene oxides such asethylene oxide, propylene oxide, butylene oxide, their mixtures and thelike.

Polyols, that is, alkylene polyols which can be used to form prepolymersinclude hydroxyl terminated compounds having at least two terminalreactive hydroxyl groups such as ethylene glycol, trimethylolpropane,glycerol, butylene glycols, hexylene glycols, pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitol, carbohydrates, sucrose,other sugars and the like, butanetriols, hexanetriols and the like.

Polyesters, which can be used instead of or in conjunction with alkylenepolyols or polyethers (polyoxyalkylene polyols) in preparing isocyanateterminated urethane prepolymers, include, for example, those formed byreacting organic aliphatic, cycloaliphatic or aromatic diorpolycarboxylic acids, or their ester forming derivatives thereof such asanhydrides, acid halides and the like with polyols. These hydroxylterminated polyesters must have at least two terminal hydroxyl groups.They can also be prepared by known transesterification methods. Thesepolyesters have molecular weights on the order of those of theaforementioned polyoxyalkylene glycols, that is, about 178 to about 5000and preferably about 600 to about 4000. Acids useful for preparing suchpolyesters include oxalic, maleic, azelaic, itaconic, citraconic,succinic, adipic, suberic, sebacic, ophthalic, isophthalic,terephthalic, and hexahydroterephthalic acids, their anhydrides and thealkyl unsaturated and halogen substituted derivatives of these acids aswell as their homologues. Other typical acids include hydroxy acidscontaining from to carbon atoms such as bydroxy palmitic acids, hydroxystearic acids, ricinoleic acid and the like. Other dibasic acids includedimer acids such as the dimerized unsaturated acids chosen from theoctadecadienoic acids preferably from the 9,12-octadecadienoic acid(linoleic acid) to form dilinoleic acids. The dilinoleic acids areprepared by the Diels-Alder reaction. Various fats and oils such ascastor oil, soybean oil and the like can also be used. Tribasic acidssuch as propane tricarboxylic acid, higher alkane tricarboxylic acids,benzene tricarboxylic acids, other aromatic tricarboxylic acids,trimeric acids of C acids, their anhydrides or the like can be used.Useful polyols for preparing the polyesters include low molecular weightpolyols such as ethylene glycol, diethylene glycol, triethylene glycol,1,4- butylene glycol, 1,6-hexanediol and their mixtures; glycerol,trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol,pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol,sucrose and the like as well as reaction products of the abovementionedpolyols with alkylene oxides such as ethylene oxide, propylene oxide,butylene oxide, their mixtures and the like.

Such polyesters must contain at least two terminal hydroxyl groups.Useful polyesters can be prepared by esterification of from about 2moles to about 1.02 moles of an alkylene glycol such as ethylene glycolwith one mole of a dicarboxylic acid such as oxalic acid. Polyestershaving molecular weights of from about 178 to about 5000 are useful inthe present invention. When polyols having more than two hydroxyl groupsor polycarboxylic acids having more than two carboxylic acid groups areemployed, the resulting polyesters will contain more than two terminalhydroxyl groups.

It is to be understood that the polyol, polyether and polyesterprepolymers described above must be terminated with unreacted, i.e.,free, or reactive isocyanate groups for subsequent reaction with thehydroxyl containing nitrogen compound and that such terminal reactiveisocyanate groups are the only reactive groups present in the prepolymermolecule.

PREPARATION OF TREATING AGENTS AND THEIR USE The hydroxyl containingnitrogen compounds and the isocyanate terminated urethane prepolymersdescribed above are interreacted to obtain new and novel urethanecompositions of matter which are useful as treating agents in thepresent invention. The hydroxyl containing nitrogen compounds andprepolymers are interracted in such proportions that all of thereactive, i.e., unreacted 16 or free isocyanate groups are reacted. Ifdesired, the hydroxyl containing nitrogen compound may be substituted inpart by an alcohol such as ethanol, isopropanol or the like.

When the treating agents are used in the form of solutions ordispersions, particularly in aqueous systems, for the treatment ofleather and the like, gelling of the final reaction product of thehydroxyl containing nitrogen compound and the prepolymer should beavoided so that treating agents having useful viscosities, solubilitycharacteristics and dispersibility characteristics, are obtained.Gelation of the final product can be controlled by selection of theratio in which the hydroxyl terminated groups in the hydroxyl containingnitrogen compounds as well as from any alcohols present are reacted withthe reactive isocyanate groups in the prepolyer. Generally, to avoidgelation, the ratio of the hydroxyl terminated groups to isocyanategroups should be not less than 2:1. Of course, an excess of hydroxylterminated groups can be present, however, this is not essential in thepresent invention. For example, in the case of a difunctionalprepolymer, that is, a prepolymer containing two reactive isocyanategroups available for reaction with the hydroxyl terminated groupspresent in the hydroxyl containing nitrogen compound, a hydroxylcontaining nitrogen compound having three hydroxyl terminated groupssuch as those shown in Formulas X and XI above is reacted with theprepolymer in a ratio of not less than six hydroxyl terminated alkanolgroups per two reactive isocyanate groups, that is, not less than twomoles of the hydroxyl containing nitrogen compound is reacted with onemole of the difunctional prepolymer. Likewise not less than three molesof the hydroxy containing nitrogen compound such as those shown inFormulas X and XI above is interreacted with one mole of a trifunctionalprepolymer, that is, a prepolymer containing three reactive isocyanategroups to avoid gelation. Additionally, to avoid gelation, at least fourmoles of the hydroxyl containing nitrogen compound such as those shownin Formulas X and XI above should be interracted with one mole of atetrafunctional prepolymer, that is, a prepolymer containing fourreactive isocyanate groups.

Where the hydroxyl containing nitrogen compound contains five hydroxylterminated groups, at least one mole of said hydroxyl containingnitrogen compound is reacted with a difunctional prepolymer, that is, aprepolymer containing two reactive isocyanate groups. When the hydroxylcontaining nitrogen compound contains seven hydroxyl terminated groups,at least one mole of the hydroxyl containing nitrogen compound isinterreacted with one mole of a trifunctional prepolymer, that is, aprepolymer containing three reactive isocyanate groups.

In cases where the hydroxyl containing nitrogen compound has only twohydroxyl terminated groups in the molecule as in the case of a hydroxylcontaining nitrogen compound derived from a monoalkanolamine such asmonoethanolarnine or N-methyl monoethanolamine, gelation is usuallyavoided by interreactiou of as little as one mole of the hydroxylcontaining nitrogen compound with each reactive isocyanate group in theprepolymer. For example, two moles of the hydroxyl containing nitrogencompound, each mole of which contains two hydroxyl terminated groups canbe interreacted with one mole of a difunctional prepolymer containingtwo reactive isocyanate groups. Likewise, three moles of the samehydroxyl containing nitrogen compound can be interreacted with one moleof a trifunctional prepolymer and four moles of the same hydroxylcontaining nitrogen compound can be interreacted with one mole of atetrafunctional prepolymer. It is to be understood that mixtures ofhydroxyl containing nitrogen compounds having varying numbers ofhydroxyl terminated groups can be reacted with mixtures of isocyanateprepolymers having varying numbers of reactive isocyanate groups.However, for those applications where it is desirable to avoid gelation,the abovementioned limitation should be observed. The final prodnet is atreating agent which is a polyurethane polymer which contains terminalhydroxy groups and does not contain reactive isocyanate groups, that is,unreacted or active or free isocyanate groups.

Treating agents can be prepared by interreaction of hydroxyl containingnitrogen compounds and isocyanate terminated urethane prepolymers forabout thirty minutes to about six hours at temperatures of from about 25to about 160 C. Such reactions are carried out under anhydrousconditions. Hydroxyl containing nitrogen compounds can be interreactedwith prepolymers by the following procedure. The required amount ofisocyanate terminated urethane prepolymer is charged into a reactorequipped with agitator and heated with agitation to a temperature offrom about 40 to about 80 C. The required amount of hydroxyl containingcompound is heated in a second reactor to a temperature of from about 40to about 80 C. The heated prepolymer is then slowly added over a periodof time from about fifteen minutes to about two hours to the heatedhydroxyl containing nitrogen compound in the second reactor while thereaction temperature is maintained at from about 40 to about 80 C. Afteraddition of the prepolymer is complete, the reaction mixture is heatedto a temperature of from about 80 to about 160 C. and maintained withinthis temperature range for about thirty minutes to about four hours tocomplete reaction. The resulting product, which is a treating agent, iscooled to room temperature. Optionally, the hydroxyl containing nitrogencompound and prepolymer can be mixed at about 25 C. and interreacted attemperatures up to about 160 C. to complete reaction. When desired, anhydrous inert solvent may be employed.

The treating agent may be used directly or may be used to preparetreating agent formulations. The agent may be reacted with acids to formsalts that are soluble or dispersible in water and/or other solvents.Inorganic acids such as hydrochloric acid, sulfuric acid, phosphoricacid, nitric acid and the like may be used to prepare salts of thetreating agents. Likewise, organic acids such as formic acid, aceticacid, propionic acid, butyric acid, isobutyric acid, succinic acid,maleic acid and the like may be used in the preparation of salts of thetreating agent. Such salts are prepared by reacting the acid andtreating agent at a temperature of from about 25 C. to about 150 C.provided such conditions do not result in decomposition of the reactantsor salts. Generally, one mole of the acid is reacted with ta least onenitrogen atom present in the treating agent. When desired, all of thenitrogen atoms can be reacted. The salts can be formed in anhydrous oraqueous systems and solvents can be employed. Organic acids which formtreating agent salts that disassociate on heating are particularlyuseful in the preparation of treating agent formulations. When desired,formulations of treating agents or their salts can be prepared withsurfactants, alcohols, chlorinated solvents and the like. Suchformulations are useful in specific applications such as padding,brushing, dipping, spraying, coating and the like.

Surfactants such as nonionic surfactants and cationic surfactants can beused in such formulations. Such surfactants include nonionic surfactantsobtained from the reaction of alkylene oxide such as ethylene oxide,propylene oxide, butylene oxide, their mixtures and the like withalkylphenols, fatty acids, alcohols and the like and cationicsurfactants such as those obtained from the reaction of alkylene oxideswith nitrogen containing hydrophobic compounds and those obtained byquaternization of nitrogen containing compounds. Useful surfactantsinclude the Pluronics which are block copolymers consisting ofpolypropylene oxide and polyethylene oxide blocks and having molecularweights of from about 600 to about 100,000. The pluronics arepolyalkylene glycol ethers. The tergitol surfactants which arepolyalkylene glycol ethers, produced by Union Carbide Corporation havingmolecular weights ranging from about 1000 to about 50,- 000 can also beused. Spans and Tweens such as sorbitan monoleate, sorbitan monolaurate,sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate,sorbitan trioleate, polyoxyethylene sorbitan monostearate,polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitanmonostearate and the like can also be used. Specific products includeSpan 20, Span 40, Span 60, Span 85, Tween 40, Tween 60 and Tween 80.Mixtures of the above surfactants can be used.

Solvents which can be employed in treating agent compositions includewater, hydrophilic alcohols such as methanol, ethanol, Z-methoxyethanol,isopropanol and the like, hydrophobic alcohols, such as octyl alcohol,decyl alco hol and the like, chlorinated solvents such as chlorinatedethylenes, chlorinated benzenes and the like and hydrocarbon solventssuch as petroleum ether, mineral spirits, benzene, toluene, xylenes,their mixtures and the like.

' When the treating agents are formulated with solvents, from about 0%by weight to about 99% by weight of solvents based on the weight of thetreating agent can be used. When the treating agents are formulated withsurfactants from about 0% by Weight to about 20% by weight ofsurfactants based on the weight of treating agent can be used.

Another embodiment of this invention includes quaternary compounds andtheir use as treating agents. These quaternaries are of two types, i.e.,those prepared by reacting either (1) the hydroxyl containing nitrogencompound or (2) the reaction products of these nitrogen compounds andprepolymers with quaternizing reagents such as methyl chloride, methylbromide, methyl iodide, ethyl chloride, benzyl chloride, dimethylsulfate and the like. Generally one mole of the quaternizing agent isreacted with at least one nitrogen atom present in the hydroxylcontaining nitrogen compound or its reaction product with a prepolymer.When desired, all of nitrogen atoms present in the hydroxyl containingnitrogen compound or its reaction product with the prepolymer can bereacted with the quaternarizing agent. The reaction is carried out undersubstantially anhydrous conditions at a temperature of from about 25 C.to about 100 C. for a period of from about one hour to about ten hours,but temperatures up to about C. can be employed provided the reactantsand products are heat stable and do not decompose. The reaction shouldbe carried out under pressure when temperatures above 100 C. are used orvolatile quaternarizing reagents are employed. When desired, an inertsolvent can be used, that is, a solvent which does not react with thequaternarizing agent. Such quaternary compounds may be used directly astreating agents or can be formulated. The surfactants and solventsdescribed above may be used in the formulation of treating agentcontaining quaternary compounds derived from the hydroxyl containingcompounds and their reaction products with the prepolymers disclosed inthe present invention.

Preparation of the hydroxyl containing nitrogen compounds, isocyanateterminated urethane prepolymers, reaction products of these compoundswith such prepolymers, quaternaries of the hydroxyl containing nitrogencompounds and their reaction products with such prepolymers aregenerally carried out at atmospheric pressure. The prepolymerpreparations are carried out under a nitrogen blanket to provideanhydrous conditions during reaction. When desired, any other inertanhydrous gas may be employed as a gas blanket to provide anhydrousconditions. Optionally, a nitrogen blanket can be used in the reactionbetween the prepolymer and hydroxyl containing nitrogen compound.Likewise, the alkoxylation of Mannich Base compounds is carried outunder substantially anhydrous conditions. Reaction of the resultinghydroxyl containing nitrogen compound and prepolymer to obtain thetreating agent is also carried out under substantially anhydrousconditions.

The treating agents disclosed in this invention are useful in thetreatment of fibrous materials such as textiles,

19 plastics, leather, paper and the like. Such agents include thehydroxyl containing nitrogen compounds, their acid addition salts, theirquaternaries, reaction products of the hydroxyl containing nitrogencompounds and isocyanate terminated urethane prepolymers, their acidaddition salts and their quaternaries.

These treating agents are useful as treating agents in the production ofleather from animal skins such as cowhides, calfskins, goatskins,horsehides, reptile skins, other animal skins and the like. As examplesof skins, which may be treated with these agents, there may be mentionedskins of freshly killed animals, limed skins, pickled skins, tannedskins, partly tanned skins, partly dechromed skins, dechromed skins andthe like. The agents can be employed as treating agents for leather,pretanning agents, tanning agents, retanning agents and impregnatingagents. They are particularly useful in the retanning of chrome stockleather. They produce retanned leathers having good break, excellenttemper and tight grain. In retanning leather, skins which have beenchrome tanned, split and shaved are used. Sides of leather vary in fiberdensity. There are looser areas in the leather, particularly in fianksections, where the fibers are long and less dense. The leather sidesare retanned to upgrade the leather and to improve its quality anduniformity, that is, to fill and firm up looser areas.

The treating agents can be used in both two-step and one-step retanningprocesses. In a conventional two-step retanning process sufiicienttreating agent is applied in the form of a solution so that from about0.1% to about 15% by weight of the treating agent based on the weight ofleather is absorbed in the pores of the leather. Usually chrome tannedstock containing 50% by weight of water based on its wrung, split shavedweight is employed. The leather is then treated with a solutioncontaining an anionic tanning agent so that from about 0.1% by weight toabout 15% by weight of the anionic tanning agent based on the weight ofthe leather is absorbed in the pores of the leather. The anionic tanningagent will then interreact in the pores with the cationic treating agentin situ in the leather to fill the pores. In a conventional one-stepretaining process, leather is treated with the reaction product of atreating agent and an anionic tanning agent so that from about 0.1% byweight to about 30% by weight of the reaction product of the treatingagent and anionic tanning agent based on the weight of leather isabsorbed and fills the pores of the leather. The treating agentsdisclosed in this invention produce excellent results in both types ofretanning processes.

As examples of anionic agents which may be used in both the two-step andthe one-step processes for retanning, there may be mentioned naphthalenesulfonic acid and formaldehyde condensation products, sulfonatedformaldehyde phenol condensation products, condensation products ofsulfonated phenol and formaldehyde, sulfonated products ofdihydroxyphenol sulfone, sulfonated products of dihydroxyphenol propane,preferably in the form of omega sulfonate forms, sulfonateddihydroxyphenyl methane, phenolic derivatives possessing aurea-formaldehyde condensation bridge or any resin intermediate as abridge formation, lignin sulfonates, vegetable tannins such as wattleextract solubilized by sodium bisulfite, quebracho extract solubilizedby sodium bisulfite, synthetic tannins known as extract tannins andhaving at least one sulfo radical and the like.

Such anionic agents include exchange tannins and auxiliary tanningagents in general. These tannins include those having sulfo groups andanionic complexes or phenol, cresol, xylenol, naphthol, catechol,resorcinol, naphthalene, anthracene and benzidine with a methylene,sulfone, propane or sulfom'mid bridge. Illustrative examples of thesecompounds are: disulfo dinaphthol methane, disulfo dinaphthyl methane,monosulfo dihydroxy diphenyl methane, a complex reaction product formedby reacting monosulfo dihydroxy diphenyl methane with formaldehyde togive the formula:

HO OH HO OH H0 S- CHr CH:- CHz SO H Omega sulfonate or dihydroxydimethyl diphenyl sulfone, omega sulfonate of dihydroxy diphenylsulfone, omega sulfonate of dihydroxy diphenyl propane, disu'lfodihydroxy diphenyl propane, disulfo dihydroxy diphenyl sulfone, andcomplex compounds containing a 'benzidine radical with asulfonimide-bridge as illustrated by the following compound can also beused:

I NH g 0311 g 03H NH The treating agents disclosed in this invention arealso useful in leather impregnation. Compositions containing from about0.1 to about 30% by weight of treating agent based on the weight ofleather can be prepared by diluting the treating agent with alcohol oralcohol-water mixtures. These compositions are used to impregnate andcondition leather which has been previously fat-liquored. Excellentpenetration of the leather with these compositions are obtained and noevidence of tackiness is noted after the impregnated leather has beendried. These compositions can be applied as spray coatings, curtaincoatings, by drum applications and the like. Chrome tanned leather aswell as vegetable tanned leather can be impregnated with thesecompositions.

Normally retanning operations are carried out at temperatures from about40 F. to about 125 F. for periods of time ranging from about thirtyminutes to about eight hours. Leather impregnation operations areusually carried out at about 40 F. to about F. Drying operations arecarried out by conventional methods.

For a fuller understanding of the nature and objects of this invention,reference may be made to the following examples which are given merelyto illustrate the invention and are not to be construed in a limitingsense. All weights, proportions and percentages are by weight unlessotherwise indicated. Likewise, all references to temperature are C.unless otherwise indicated.

EXAMPLE I (A) Preparation of a Mannich Base compound.

315 g. (3 mole) of diethanolamine and 60 g. of methanol were chargedinto a glass flask equipped with agi tator, reflux condenser andprovisions for external heating. The charge was cooled to about 10 C.and 244.5 g. (3 moles) of aqueous formaldehyde (37% by weight active)was added at about 10 C. to about 15 C. slowly with agitation over sixtyminutes. After addition was complete, a mixture of 282 g. (3 moles) ofphenol and 25 g. of methanol was added at about 18 C. to about 22 C.over fifteen minutes with vigorous agitation. The

21 resulting reaction mixture was agitated at about 18 C. to about 22 C.for one hour, heated to about 65 C. and agitated at about 65 C. for twohours to complete reaction.

The resulting reaction product which was the desired Mannich Basecompound was then vacuum distilled to remove water, methanol and othervolatile materials. Vacuum distillation was continued with heating untila pot temperature of 100 C. was reached. The reaction product was thenheld under vacuum at 100 C. for fifteen minutes and then cooled to 30 C.Analysis showed the water content of the Mannich Base compound was 0.5%by weight and the compound contained three hydroxyl groups, that is, onephenolic hydroxyl and two alkanol hydroxyl groups.

(B) Preparation of a hydroxyl containing nitrogen compound A total of211 g. (1 mole) of the Mannich Base compound obtained in part (A) abovewas charged into a glass flask equipped with agitator, reflux condenserand provisions for maintaining a nitrogen blanket over the compound andfor external heating and cooling. The Mannich Base compound was heatedto 95 C. with agitation under a nitrogen blanket. Propylene oxide wasthen introduced under the nitrogen blanket and condensed with theMannich Base compound at a temperature of about 95 C. to about 110 C. toform the hydroxyl containing nitrogen compound which was a propoxylatedadduct of the Mannich Base compound. Propylene oxide addition wascontinued under the above described conditions until a total of 116 g.(2 moles) of propylene oxide had reacted with the Mannich Base compound,that is, a total of two moles of propylene oxide was condensed with onemole of the Mannich Base compound. The resulting adduct of propyleneoxide and Mannich Base compound was an aromatic polyol containing threeterminal hydroxyl groups which consisted of two alkanol groups attachedto a nitrogen atom and a hydroxyalkyl phenoxy group wherein the threehydroxyl groups had been partially reacted with propylene oxide, PrO,that is, 3 OH/ 1 Pr.O.

(C) Preparation of an isocyanate terminated urethane prepolymer (for usein subsequent examples) 1540 g. (1 mole) of a polyethylene glycol havingan average molecular weight of 1540 was charged into a glass flaskequipped with agitator, external heating and cooling facilities as wellas provision for maintaining a nitrogen blanket over the reactants toprovide anhydrous conditions during reaction. The polyethylene glycolwas a solid and was heated to a temperature slightly above its meltingpoint to liquefy the glycol.

348 g. (2 moles) of tolylene diisocyanate was added with agitation tothe melted glycol over fifteen minutes. The reaction mixture was thenheated with agitation to 70 C. and agitated at about 70 C. to about 75C. for forty-five minutes to obtain an isocyanate terminated urethaneprepolymer which has a reactive isocyanate content of 4.36% by weight.

EXAMPLE II (A) Preparation of a Mannich Base compound 2967 g. (28.2moles) of diethanolamine and 1250 g. of Water were introduced into areaction vessel equipped with agitator and were agitated with cooling.When the temperature of the diethanolamine mixture reached about 8 C. toabout 10 C., a mixture of 2303 g. (28.6 mols) of aqueous formaldehyde(37% by weight active) and 1250 .g. of water at about 10 C. wereintroduced over a period of one and one-half hours with good agitation.The temperature was maintained at about 10 C. during this addition. Amixture of 1328 g. 14.1 moles) of phenol and 117 g. of water was thenintroduced at about 10 C. over twenty minutes with agitation. Theresulting 22 reaction mixture was then agitated for an additional hourat about 10 C. 785 g. of methanol was then added to the reaction mixtureand the resulting mixture was heated to about C. to about C. and stirredat about 65 C. for two hours. Water, methanol and other volatilematerials present in the reaction mixture were then removed by vacuumdistillation. The reaction mixture was slowly heated under vacuum toabout C. to about 110 C. The reaction mixture was then held for fifteenminutes at about 110 C. under full vacuum and then cooled to roomtemperature. The reaction product remaining in the flask was a MannichBase compound having a water content of about 0.2% by weight andcontaining five terminal hydroxyl groups, that is, one phenolic hydroxylgroup and four alkanol hydroxyl groups.

(B) Preparation of a hydroxyl containing nitrogen compound 328 g. (1mole) of the Mannich Base compound obtained in part (A) above wasintroduced into a glass flask equipped with agitator, reflux condenserand provisions for maintaining a nitrogen blanket over the compound andfor external heating and cooling. The Mannich Base compound was heatedwith agitation to about 95 C. under a nitrogen blanket and 58 g. (1mole) of propylene oxide was introduced under the nitrogen blanket andcondensed with the Mannich Base compound at a temperature of about 95 C.to about 110 C. An additional 87 g. (1.5 mole) of propylene oxide wasthen introduced to the reaction mixture and reacted at about C. to aboutC. The resulting product was a hydroxyl containing nitrogen compoundwhich was the adduct of one mole of the Mannich Base compound and 2.5moles of propylene oxide and contained five terminal hydroxyl groups,that is, four terminal alkanol hydroxyl groups and one hydroxyalkylphenoxy group wherein the five hydroxyl groups had been reacted with 1.5moles of propylene oxide, PrO, that is 50H/ 1.5 PrO.

EXAMPLE III (A) Preparation of a Mannich Base compound A mixture of 945g. (9 mole) of diethanolamine and 390 g. of distilled water was chargedinto a glass flask equipped with agitator, reflux condenser andprovisions for external heating and cooling. The charge was cooled toabout 10 C. and 733.5 g. (9.05 mole) of aqueous formaldehyde solution(37% by weight active) and 398 g. of Water was added slowly at about 10C. to about 15 C. with agitation over a period of one hour. Theformaldehyde and water solution was adjusted to a pH of 8.0 with sodiumhydroxide solution prior to its addition to the diethanolamine solution.After reaction was complete, a mixture of 423 g. (4.5 moles) of phenoland 37.5 g. of water was added at about 10 C. to about 14 C. overfifteen minutes with vigorous agitation. The resulting reaction mixturewas then agitated at about 10 C. to about 14 C. for one hour. 250 g. ofmethanol was then added and the reaction mixture was agitated andgradually heated to about 65 C. The reaction mixture was then heated atabout 65 C. for two hours to complete reaction. The resulting reactionproduct which was the desired Mannich Base compound was then vacuumdistilled to remove water, methanol and other volatile materials. Vacuumdistillation with heating was continued until a pot temperature of about100 C. was reached. The Mannich Base compound was then held under fullvacuum at about 100 C. for fifteen minutes and cooled to about 30 C.Analysis showed that the water content of the Mannich Base compound was0.17% by weight. The Mannich Base compound contained five terminalhydroxyl groups, that is, one phenolic hydroxyl group and four alkanolhydroxyl groups.

(B) Preparation of a hydroxyl containing compound A total of 328 g. (1mole) of the Mannich Base compound obtained in part (A) above wascharged into a glass flask equipped with agitator, reflux condenser andprovisions for maintaining a nitrogen blanket over the reactants and forexternal heating and cooling. The Mannich Base compound was heated toabout 95 C. with agitation and under a nitrogen blanket. Propylene oxidewas then introduced under the nitrogen blanket and condensed with theMannich Base compound at about 95 C. to about 110 C. until a total offive moles of propylene oxide had been condensed with one mole of theMannich Base compound. The adduct contained five terminal hydroxylgroups, that is, four terminal hydroxyl groups and one hydroxyalkylgroup wherein the five hydroxyl groups had been reacted with 4 moles ofpropylene oxide, PrO, that is, 50H/4P'r0.

EXAMPLE IV (A) Preparation of a Mannich Base compound A mixture of 420g. (4 moles) of diethanolamine and 180 g. of distilled water was chargedinto a glass flask equipped with agitator, reflux condenser andprovisions for external heating and cooling. The diethanolamine mixturewas cooled to about C. A solution containing 326 g. (4.02 moles) ofaqueous formaldehyde (37% by weight) and 180 g. of distilled water whichhad been neutralized to a pH of 8.1 with 30 B. sodium hydroxide solutionwas prepared. The formaldehyde solution was slowly added with agitationat a temperature of about 10 C. to about C. over a period of one hour.After addition of the formaldehyde solution was complete, 880 g. (4moles) of nonylphenol was added at about 10 C. to about 16 C. over aperiod of about fifteen minutes with vigorous agitation. The resultingreaction mixture was then agitated for one hour at about 10 C. to about16 C. 933.3 g. of methanol was then added to the reaction mixture andthe reaction mixture was heated to about 65 C. and agitated at about 65C. for two hours to complete reaction. The resulting product which wasthe Mannich Base compound was then vacuum distilled to remove water,methanol and other volatile materials. Vacuum distillation was continuedwith heating until a pot temperature of about 100 C. was reached. TheMannich Base compound was then held under full vacuum at about 100 C.for fifteen minutes and then cooled to about 30 C. to obtain a compoundcontaining 0.5% by weight water. The Mannich Base compound containedthree hydroxyl groups, that is, one phenolic hydroxyl group and twoalkanol hydroxyl groups.

(B) Preparation of a hydroxyl containing nitrogen compound A total of337 g. (1 mole) of the Mannich Base compound obtained in part (A) abovewas charged into a glass flask equipped with agitator, reflux condenserand provisions for maintaining a nitrogen blanket over the reactants andfor external heating and cooling. The Mannich Base compound was thenheated with agitation to about 95 C. under a nitrogen blanket. Propyleneoxide was then introduced under the nitrogen blanket and condensed withthe Mannich Base compound at about 95 C. to about 110 C. to form thedesired hydroxyl containing compound which was a propoxylene oxideadduct of the Mannich Base compound. Propylene oxide addition wascontinued until a total of 116 g. (2 mole) of propylene oxide hadcondensed and reacted with one mole of the Mannich Base compound. Thehydroxyl containing nitrogen compound was the condensate of two moles ofpropylene oxide with one mole of the Mannich Base compound and containedthree hydroxyl groups, that is, one hydroxyalkyl phenoxy group and twoalkanol hydroxyl groups which had been partially reacted with one moleof propylene oxide, PrO, that is, 30H/1Pr0.

(C) Preparation of a treating agent To 453 g. (1 mole) of the hydroxylcontaining nitrogen compound obtained in part (B) above was introduced126 g. (1 mole) of dimethyl sulfate over a period of two hours while thereaction temperature was maintained at about 45 to about 55 C. Afterdimethyl sulfate addition was complete, the reaction mixture wasagitated for three hours at about 50 C. to complete the reaction. Thereaction product was a quaternary ammonium salt which was useful as atreating agent. 579 g. of distilled water was added to the reactionproduct with agitation and stirred for one hour at about 50 C. to obtaina 50% by weight solution of the quaternary treating agent.

EXAMPLE V (A) Preparation of a treating agent 240.8 g. (0.128 mole) ofthe urethane prepolymer obtained in part (C) above of Example I wascharged into a glass flask and heated to its melting point. After theprepolymer was completely melted. 82 g. (0.252 mole) of the hydroxylcontaining nitrogen compound obtained in part (B) of Example I was mixedwith the molten prepolymer and heated to a temperature of about C. toabout C. The resulting mixture was reacted for ninety minutes at about90 C. to about 95 C. to obtain a treating agent which was designated asTreating Agent D. 322.8 g. of the treating agent obtained above wasdiluted with 307.8 g. of water and 15 g. of glacial acetic acid toobtain a 5 0% active solution of Treating Agent D.

(B) Preparation of a treating agent 240.8 g. (0.128 mole) of theisocyanate terminated urethane prepolymer obtained in part (C) ofExample I above was charged into a glass flask and heated to its meltingpoint. After the prepolymer was completely melted 82 g. (0.252 mole) ofthe hydroxyl containing nitrogen compound obtained in part (B) ofExample I above was mixed with the molten prepolymer and heated to atemperature of about 90 C. to about 95 C. The resulting reaction mixturewas reacted at about 90 C. to about 95 C. for ninety minutes to obtain atreating agent which was designated as Treating Agent E. A solution ofTreating Agent E was prepared by mixing 322.8 g. of a 40% by weightsolution of the disodium salt of disulfo dinaphthyl methane, 322.8 g. ofTreating Agent E and 322.8 g. of water. The resulting solution ofTreating Agent E was 33.33% by weight active, that is, it contained thispercentage of Treating Agent E.

EXAMPLE VI Use of a treating agent in leather retanning lbs. of shavedchrome stock leather based on the chrome tanned split shaved weight wasput in a drum and wet back for thirty minutes in a 200% float at 100 F.All percentages including those for floats are as percent by weightbased on the shaved chrome stock leather weight. The pH of the liquorwas 3.4. The liquor was drained off and the chrome stock floated in 200%water. by weight of sodium bicarbonate was added to the drum in twofeeds at twenty minute intervals. The pH of the liquor after bicarbonateaddition was 4.1. The stock was then washed in a 200% float at 1 10 F.for ten minutes and drained. A 50% float containing 5% by weight of the50% solution of Treating Agent D described in Part (A) of Example Vabove was added. The leather was run for one hour at F. The pH of thefloat was 4.4. The float was drained and a new 50% by weight floatcontaining 5% by Weight of a synthetic replacement tannin which was thecondensation product of urea, formaldehyde and sulfonated oresol wasadded. This float was run for one hour at 110 F. During this period, thecationic Treating Agent D interreacted with the replacement tannin whichwas an anionic tanning agent. The drained chrome stock was then washedin a 200% float for five minutes at F.

The washed treated leather was than fat-liquored in a 100% floatcontaining sulfated vegetable and animal oils at 120 F. for forty-fiveminutes. After fat liquoring, the leather was drained, horsed and dried.The finished leather showed a tight grain effect and had excellenttemper.

EXAMPLE VII Use of a treating agent in leather retanning 100 lbs. ofshaved split chrome stock based on the chrome tanned split shaved weightwas placed in a drum and wet back for thirty minutes with a 200% Waterfloat at 100 P. All percentages including those for floats are aspercent by Weight based on the shaved split chrome stock weight. The pHof the liquor was 4.2. After draining the liquor, the chrome stock wasfloated in 200% water. Then /s% by weight of sodium bicarbonate wasadded in one feed and the leather was run for thirty minutes. The pH ofthe liquor was 4.0. The stock was then washed in a 200% float at 110 F.for ten minutes and drained. A 50% by weight new float containing byweight of the 33.33% solution of Treating Agent E described in Part (B)of Example V above was then added. The float was run for one hour at 110F. by weight of formic acid was added to the float in one feed and runfor fifteen minutes. The pH of the liquor was 3.6. The treated chromestock was then washed with water for five minutes at 120 F. A 100% byweight float containing 5% sulfated vegetable and animal oils based onthe weight of water was added and the retanned leather fat liquored forforty-five minutes at 120 F. After fat liquoring, the leather wasdrained, horsed up and dried. The finished leather showed tight grainand had excellent temper.

EXAMPLE VIII (A) Preparation of a Mannich Base compound Into a glasslined kettle equipped with agitator, reflux condenser and provisions forcooling and heating, a mixture of 34.00 lbs. (0.324 mole) ofdiethanolamine and 6.48 lbs. of methanol was introduced. The mixturecooled to about 10 C. and 26.38 lbs. (0.33 mole) of aqueous formaldehydesolution (37% by weight active) was then slowly added over one hourwhile the temperature was maintained at about 10 C. to about C. Amixture of 30.44 lbs. (0.32 mole) of phenol and 2.70 lbs. of methanol ata temperature between about C. and about C. was added with continuousstirring. This addition was made as a single feed. Cooling was removedand the temperature of the reaction mixture was allowed to rise to about20 C. to about 25 C. The reaction mixture was then heated to raise thetemperature to about 60 C. to about 65 C. Approximately two hours wasrequired to heat the reaction mixture to about 65 C. The reactionmixture was then vacuum distilled to remove water, methanol and othervolatile materials. The temperature was gradually raised during vacuumdistillation until a final temperature of about 105 C. was reached. Thereaction mixture was heated at about 105 C. for about fifteen minutesand then cooled to room temperature. The reaction product was thedesired Mannich Base compound and contained about 0.3% water by Weight.The Mannich Base compound contained three hydroxyl groups, that is, onephenolic hydroxyl group and two alkanol hydroxyl groups.

(B) Preparation of a hydroxyl containing nitrogen compound 21.1 lbs.(0.1 mole) of the Mannich Base compound obtained in part (A) above wascharged into a glass flask equipped with agitator, reflux condenser andprovisions for maintaining a nitrogen blanket over the reactants and forexternal heating and cooling. The Mannich Base compound was heated withagitation to about 95 C. under a nitrogen blanket. 14.5 lbs. (0.25 mole)of propylene PrO, that is, 30H/ 1.5 PrO.

EXAMPLE IX (A) Preparation of an isocyanate terminated urethaneprepolymer 1527 g. of a polypropylene glycol having an average molecularweight of 1025 and an average hydroxyl value of 110.2 was mixed with 522g. of tolylene diisocyanate under a nitrogen blanket and heated withstirring to a temperature of about C. An exothermic reaction occurred atabout 65 C. and heating was discontinued. The temperature gradually roseto a temperature of about 75 C. during the exothermic reaction. Thereaction mixture was heated with agitation at about 75 C. to about 80 C.for a period of one hour. After heating for one hour at about 80 C., thereaction product which was an isocyanate terminated urethane prepolymerwas cooled to room temperature. Analysis showed that the reactionproduct had a reactive isocyanate content of 6.0% by weight.

(B) Preparation of a treating agent 338.7 g. of the isocyanateterminated urethane prepolymer obtained in part (A) above of thisexample and 163.5 g. of the hydroxyl containing nitrogen compoundobtained in part (B) of Example I above were mixed under a nitrogenblanket in a flask and were heated to a temperature of about C. Thecharge was then reacted under the nitrogen blanket at a temperature ofabout 70 C. to about C. for ninety minutes to complete reaction. Thereaction product was a treating agent, that is, a polyurethane resin.188 g. of anhydrous isopropanol was added to the treating agent and themixture stirred to obtain a uniform solution. The solution was thencooled to about 65 C. and 63 g. of dimethyl sulfate was added to thesolution over a period of about two hours. The temperature during thedimethyl sulfate addition was maintained at a temperature of from about65 C. to about 70 C. during the addition. The resulting reaction productwas a quaternary ammonium derivative of the treating agent which wasuseful as a treating agent. The quaternary ammonium derivative was awater-soluble treating agent which exhibited strong cationic activity.

EXAMPLE X Preparation of a treating agent 677 g. of the isocyanateterminated urethane prepolymer obtained in part (A) of Example IX aboveand 327 g. of the hydroxyl containing nitrogen compound obtained in part(B) of Example I above were mixed and reacted by the procedure describedin part (B) of Example IX above to obtain a treating agent which was apolyurethane resin. 200 g. of 1,4-dioxane was added to the resin and 60g. of glacial acetic acid and 864 g. of water were then added to obtaina solution of the treating agent. The resulting solution contained acationic salt of the treating agent which was soluble in water andexhibited strong cationic activity.

EXAMPLE XI (A) Preparation of an isocyanate terminated urethaneprepolymer 874.8 g. of polypropylene glycol having an average molecularweight of 425 and an average hydroxyl value of 256.4 was mixed with 696g. of tolylene diisocyanate 27 under a nitrogen blanket. The resultingmixture was heated with stirring under the nitrogen blanket to atemperature of about 65 C. Heating was discontinued when the reactiontemperature reached about 65 C. An exothermic reaction occurred at about65 C. and the temperature gradually rose to a temperature of about 75 C.The reaction mixture was reacted at a temperature of about 75 C. toabout 80 C. for one hour with stirring and heating. After this period,heating was discontinued and the reaction product which was anisocyanate terminated urethane prepolymer was cooled to roomtemperature. Analysis showed that the urethane prepolymer had a reactiveisocyanate content of about 10.4% by weight.

(B) Preparation of a treating agent 403 g. of the isocyanate terminatedurethane prepolymer obtained in part (A) above of this example was mixedunder a nitrogen blanket with 327 g. of the hydroxyl containing nitrogencompound obtained in part (B) of Example I above. The mixture was thenheated to about 70 C. and reacted at about 70 C. to about 75 C. underthe nitrogen blanket with agitation for a period of about one hour. Theresulting reaction product was a polyurethane resin which was useful asa treating agent. 60 g. of glacial acetic acid were added to thetreating agent to obtain a solution which was then diluted with 790 g.of water. This solution of the treating agent contained a water-solublecationic salt of the treating agent which exhibited strong cationicactivity.

EXAMPLE XII Preparation of a treating agent 90.8 g. of the isocyanateterminated urethane prepolymer obtained in part (A) of Example XI and65.4 g. of the hydroxyl containing nitrogen compound obtained in part(B) of Example I above were mixed under a nitrogen blanket in a flaskand were heated with stirring to a temperature of about 65 C. to about70 C. The mixture was reacted at this temperature for about one hourwith stirring to obtain the treating agent which was polyurethane resin.150 g. of anhydrous isopropanol was added to the treating agent and themixture stirred to obtain a uniform clear solution. The isopropanolsolution was then heated to about 65 C. to about 70 C. with stirring and25.2 g. of dimethyl sulfate was added over about one hour at thistemperature. The resulting reaction product was a quaternary ammoniumsalt of the treating agent. The quaternary treating agent waswater-soluble and exhibited strong cationic activity.

EXAMPLE XIII Use of a treating agent in leather retanning 100 lbs. ofshaved chrome leather stock based on the chrome tanned split shavedweight was put in a drum and wet back for thirty minutes in a 200% floatat 100 F. All percentages including those for floats are as percent byweight based on the chrome tanned split shaved stock weight. The pH ofthe liquor was 3.5. The liquor was drained off and the stock floated in100% water at 100 F. 1% by weight of sodium formate was added to theliquor in the drum and the stock was run for thirty minutes. The pH ofthe liquor was 3.9. The liquor was drained off. A 50% float containing5% by weight of the quaternary treating agent described in part (B) ofExample IX above based on the chrome tanned split shaved weight wasadded to the stock in the drum. The stock was run in the drum for thirtyminutes at 110 F. 5% by weight of a dry synthetic replacement tanninwhich was the condensation product of urea, formaldehyde and sulfonatedcresol was added to the liquor in the drum and the drum was run forthirty minutes at 110 F. The pH of the liquor was 4.0. 0.5% by weight offormic acid was added in one feed to the liquor in the drum and thestock was run for fifteen minutes. The pH of the liquor was 3.4. Theliquor was drained. The treated chrome stock was washed for five minutesat 120 F. in a 300% float and the liquor drained. A new float was addedto the treated chrome stock. 3% by weight of a fat liquor, which was aactive emulsifiable neatsfoot oil, and 0.1% Sterezol S Germicide(Wallerstein Co., Staten Island, N.Y.), which was a mixture of pine oil,cresols, orthophenylphenol, pentachlorophenol and betanaphthol, wereadded to the float. The retanned leather was treated with this float forthirty minutes at 120 F. The pH of the liquor was 3.8. After this finaltreatment, the stock was drained, horsed and. dried. The finishedleather had tight grain and excellent temper.

EXAMPLE XIV Use of a treating agent in leather retanning lbs. of shavedchrome leather stock based on the chrome tanned split shaved weight wasput in a drum and wet back for thirty minutes in a 200% float at 100 F.All percentages including those for floats are as percent by weightbased on the chrome tanned split shaved stock weight. The pH of theliquor was 3.5. The liquor was drained off and the stock was floated in100% water at 100 F. 1% by weight of sodium formate was added to theliquor in the drum and the stock was run for thirty minutes. The pH ofthe liquor was 3.9. The liquor was drained off. A 50% float containing3% by weight of a fat liquor, which was a 80% active emulsifiablesynthetic triglyceride, was added to the stock and the float run forthirty minutes at F. The liquor was drained. A new 5 0% float containing5% by weight of the quaternary treating agent described in Example XIIabove based on the chrome tanned split shaved weight was added to thestock. The new float was run for thirty minutes at 110 F. and 5% byweight of dry synthetic replacement tannin, which was the condensationproduct of urea, formaldehyde and sulfonated cresol, was added to thefloat. This float was then run one hour at 110 F. The pH of the liquorwas 4.0. 0.5% by weight of formic acid was added in one feed to theliquor in the drum and the stock was run for fifteen minutes. The pH ofthe liquor was 3.3. The liquor was drained from the stock. The treatedchrome stock was then washed for five minutes at F. in a 300% float andthe float drained. A new 75% float was added to the treated chromestock. 3% by weight of a fat liquor, which was a 90% active emulsifiableneatsfoot oil, and 0.1% Sterezol S Germicide (Wallerstein Co., StatenIsland, N.Y.), which was a mixture of pine oil, cresols,orthophenylpheuol, pentachlorophenol and bentaphthol, were added to thefloat. The retanned leather was treated with this float for thirtyminutes at 120 F. The pH of the liquor was 3.8. After this finaltreatment, the stock was drained, horsed and dried. The finished leatherhad tight grain and excellent temper.

EXAMPLE XV Preparation of a treating agent and its use as a coating andimpregnating agent for various substrates 450 g. of the hydroxylcontaining nitrogen compound described in part (B) of Example IV abovewas dissolved in 500 g. of xylene. 680 g. of the isocyanate terminatedprepolymer described in part (A) of Example IX above was added to thexylene solution of the hydroxyl containing nitrogen compound. Theresulting mixture was reacted for about one hour at about 70 C. to about75 C. under anhydrous conditions and under a nitrogen blanket. Theresulting reaction product was cooled to room temperature and designatedas Component A.

A 50% by weight xylene solution of the prepolymer described in part (A)of Example IX above was prepared by dissolving 272 g. of the prepolymerin xylene. This xylene solution was designated as Component B.

Component A and Component B were mixed together to obtain a solution oftreating agent. It was found that the solution of treating agent wasexcellent for coating surfaces and impregnating substrates. The treatingagent formed excellent coatings on metals and wood when it was appliedand then cured for about five minutes at 325 F. in an oven. The coatingswere flexible, durable and abrasion resistant. Likewise, the treatingagent was excellent lfor impregnating substrates such as wood andfibers. The impregnated substrates were cured in the same manner as thecoated substrates. When desired, lower curing temperatures such as 200F. can be used provided longer curing times are employed, that is, tenminutes or more.

The treating agent solution had a shelf life of about seven hours atroom temperature, that is, its properties as coating agent andimpregnating agent were not adversely alfected. When desired, pigmentsand/or dyes can be added to the treating agent solution.

The excellent coating and impregnating properties or the treating agentwere attributed to reaction of all of the hydroxyl groups present in thehydroxyl containing nitrogen compound with reactive groups present inthe prepolymer. This reaction results in high polymeric reactionproducts having excellent coating and impregnating properties. Suchproperties included abrasion resistance, high gloss, high solventresistance and flexibility. This treating agent has excellent propertiesfor use as a coating and impregnating agent for textile materials suchas fibers, fabrics and the like.

EXAMPLE XVI Preparation of a treating agent and its use as a sealant andcoating 340 g. of the Mannich Base compound described in part (A) ofExample IV above and 300 g. of Shell diepoxide 828, which is thediglycidyl derivative of 4,4-dihydroxydiphenyl-dimethyl methane, weremixed and heated with agitation for about one hour at about 95 C. toabout 100 C. The reaction mixture was then heated to about 125 C. toabout 130 C. and reacted within this temperature range :for about toabout minutes to pro duce a hydroxyl containing nitrogen compound. Theresulting hydroxyl containing nitrogen compound was cooled to about 80C. 500 g. of xylene was added to the compound and stirred to obtain auniform clear solution.

670 g. of the isocyanate terminated urethane prepolymer described inpart (A) of Example IX above was added to the xylene solution ofhydroxyl containing nitrogen compound. The resulting mixture was reactedat about 70 C. to about 75 C. for one hour under anhydrous conditionsand under a nitrogen blanket. The resulting reaction product wasdesignated as Component A.

267 g. of the isocyanate terminated urethane prepolymer described inpart (A) of Example 1X above was dissolved in 267 g. of xylene. Thissolution was designated as Component B.

Component A and Companent B were mixed to obtain a treating agent. Thetreating agent was allowed to react for about three hours at about 65 F.to cure. The cured product was a solid. When this treating agent wasapplied to a substrate (wood) and then cured and the solvent removed,the cured coatings were flexible, had good adhesion to the substrate andhave abrasion resistance. If desired, dyes and/or pigments can be addedto the treating agent to form colored or pigmented coatings.

Component A and Componene B were also prepared without the use ofsolvents such as xylene. The components were heavy pastes. These twocomponents were mixed at room temperature to obtain a treating agent.The treating agent was immediately applied as a sealant to a jointbetween two pieces of wood and cured at about 60 F. for about threehours. The cured seal was excellent. The treating agent was also anexcellent sealant for metal-to-wood and metal-to-metal joints. Thetreating 30 agent was also used as an adhesive for metal-to-metal,fiber-to-fiber and wood-to-wood bonds. It gave excellent results as anadhesive.

What is claimed is:

1. A process for treating leather comprising applying from aqueousmedium to leather at from about 40 F. to about F. from about 0.1% byweight to about 30% by weight of a treating agent based on the weight ofsaid leather, said agent being selected from the group consisting of:

(I) a treating agent which is the condensation reaction product of (A) ahydroxyl containing nitrogen compound which is the reaction product of(1) a Mannich Base compound which is the reaction product of (a) aphenol having at least one reactive hydrogen atom present in the phenolnucleus, (b) at least one aldehyde selected from the group consisting ofan aldehyde and aldehyde liberating compositions, and (c) at least onealkanolamine selected from the group consisting of monoalkanolamine anddialkanolamine wherein the alkylene group of said alkanolamine has atleast two carbon atoms, said (b) and (0) being present in approximatelyequimolar amounts with respect to each other and being present insufficient amounts to react with at least one reactive hydrogen atom insaid phenol nucleus, there being present one mole of each of said (b)and (c) tfOI each reacting reactive hydrogen atom, and (2) at least onemole of an alkylene oxide containing from two to 57 carbon atoms perphenolic hydroxyl group present in said Mannich Base compound, and

(B) an isocyanate terminated urethane prepolymer which is the reactionproduct of an organic polyisocyanate and at least one member selectedfrom the group consisting of a polyol, a polyether and a polyester eachhaving at least two terminal hydroxyl groups, and

(II) a treating agent which is the condensation reaction product of (A)the reaction product of (1) a hydroxyl containing nitrogen compoundwhich is the reaction porduct of (a) a Mannich Base compound which isthe reaction product of (1) a phenol having at least one reactivehydrogen atom present in the phenol nucleus, (2) at least one aldehydeselected from the group consisting of an aldehyde and aldehydeliberating compositions, and (3) at least one alkanolamine selected fromthe group consisting of monoalkanolamine and dialkanolamine wherein thealkylene group of said alkanolamine has at least two carbon atoms, said(2) and (3) being present in approximately equimolar amounts withrespect to each other and being present in suflicient amounts to reactwith at least one reactive hydrogen atom in said phenol nucleus, therebeing present one mole of each of said (2) and (3) for each reactingreactive hydrogen atom, and (b) at least one mole of an alkylene oxidecontaining from two to 57 carbon atoms per phenolic hydroxyl grouppresent in said Mannich Base compound, and (2) an isocyanate terminatedurethane prepolymer which is the reaction product of an organicpolyisocyanate and at least one member selected from the groupconsisting of a polyol, a polyether and a polyester each having at leasttwo terminal hydroxyl groups, and (B) a member of the group consistingof acid and quaternizing reagent present in an amount suf- 31 32 ficientto react with at least one nitrogen atom 5, Leather produced by theprocess of claim 2.

present in said (A), to produce an acid addition 6. Leather produced bythe process of claim 3. salt or a quaternary ammonium salt. 2. Theprocess of claim 1 in which from about 0.1% to References Cited about15% by weight, based on the weight of the leather, 5 UNITED STATESPATENTS of at least one of the group consisting of amomc ex- 3,462,2378/1969 Sena 8 94'21 change tannins and anionic auxiliary tanning agentsis applied subsequent to application of the treating agent. 3491O671/1970 Senet 26O 75 3. The process of claim 1 in which from about 0.1% iw to about 30% by weight, based on the weight 015 the 10 GEORGE pnmaliyExmnar leather, of at least one of the group consisting of anionic H.WOLMAN, Assistant EXamlflel' exchange tannins and anionic auxiliarytanning agents is applied simultaneously with application of thetreating agent. 8-94.24, 94.27, 94.32, 94.33; l17142 4. Leather producedby the process of claim 1. 15

age UNITED STATES PATENT OFFECE CERTIFICATE @F CGRRECTWN Patent No. 3.67ii Date Julv i. 1972 Inventor(s) Lucien Sel let It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column l, after line 7, insert "assignor to Diamond ShamrockCorporation, a corgoration of Delaware". Column 2 line 9, change"aldehyde"- lst 000. i o'c wcc Column 3, replace line 32 with "nitrogencompounds. Such hydroxyl containing nitrogen". Column i, line &5, change"ban" to --been--. Column 8, l ine 3, after "in" insert --a--. Column 9,Formula (XI) that portion of the formula reading R (R O) H R 0 (R 0) HCH N should read CH --N R (R o) H R20 (R o) H Column 12, line 32, change"(65/o 2, 2,6)" to "(80% 2,- i; 20% 2,6)--; column i2, line 55, change"2, i-diisocyanatostiblene to -2, i- -diisocyanatostilbene-. Column l l,line 2 change "naphthylenediamines" to --naph thylenediamine--; column il, line 29, change "fluorenamino" to --Fluorenami ne--; column l -l,line 69, change "includes" to i ncl ude Column 17, line change "ta" to--at--. Column l9 line 57, change "d i hydroxyphenol \to--dihydroxydiphenyl-; column l9, line 59, change "dihydroxyphenyl" to,--dihydroxydiphenyl-. Column 29, line 67, change "Componene" to--Component column 29, l ine 73, change "F." to "F. Column 30, l ine 5,change "porduct" to --product--.

Signed andsealed this 19th day of March 19 74.

(SEAL) Attest:

EDWARD MPLETCHERJR; C. MARSHALL DANN Attesting Officer Commissioner ofPatents--

